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Kinetics of the solvolysis of [Co(3Rpy)4Cl2]+ ions (R = Me or Et) in Water + t-butyl alcohol mixtures

✍ Scribed by Gehan M. El-Subruiti; Cecil F. Wells; Ibrahim M. Sidahmed

Publisher: John Wiley and Sons
Year: 1992
Tongue: English
Weight: 687 KB
Volume: 24
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550240606

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✦ Synopsis

Abstract

Rates of solvolysis of complex ions [Co(3Rpy)~4~Cl~2~]^+^ with R = Me and Et have been determined in mixtures of water with t‐butyl alcohol over a range of temperatures. Extrema found in the enthalpy Δ__H__* and entropy Δ__S__* of activation are correlated with the physical properties of the solvent mixtures which are influenced by changes in the solvent structure and these extrema are compared with those found for the solvolysis of related complexes in water + alcohol mixtures. Isokinetic plots over wide ranges of Δ__H__* and Δ__S__* are compared for the solvolysis of Co^III^ complexed to a variety of ligands. The application of a free energy cycle shows that the emergent cobalt (III) cation in the transition state becomes increasingly stabilized in water‐rich mixtures relative to the cobalt (III) cation in the initial state as the mol fraction of t‐butyl alcohol increases.

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